<sup>230</sup>Th/U Isochron Dating of Cryogenic Cave Carbonates

Abstract. Cryogenic Cave Carbonates (CCCs) are a type of speleothem, typically dated with 230Th/U disequilibrium methods, that provide evidence of palaeo-permafrost conditions. In the field, CCCs occur as distinct patches of millimetre- to centimetre-sized loose crystals and crystal aggregates on the floor of cave chambers, lacking a framework to validate ages by stratigraphic order. Correction factors for initial 230Th (230Th0) are often based on the bulk-earth derived ratio of initial 230Th/232Th activity ((230Th/232Th)0), which is a well-established approach when 230Th0 is moderately low. For samples with elevated levels of 230Th0, however, accuracy can be improved by constraining (230Th/232Th)0 independently. Here, we combine detailed morphological observations from three CCC patches found in Water Icicle Close Cavern in the Peak District (UK) with 230Th/U analyses. We find that individual CCC crystals show a range of morphologies that arise from non-crystallographic branching in response to the chemical evolution of the freezing solution. Results of 230Th/U dating indicate that samples with a large surface area relative to the sample volume are systematically more affected by contamination with 230Th0. By fitting isochrons to these results, we test whether the CCCs in an individual patch formed during the same freezing event, and demonstrate that (230Th/232Th)0 can deviate substantially from the bulk-earth derived value and also vary between the different CCC patches. Where CCCs display elevated 230Th0, isochrons are a useful tool to constrain (230Th/232Th)0 and obtain ages with improved accuracy. Detritus absorbed to the crystal surface is shown to be the most likely source of 230Th0. Our results suggest that some previously published CCC ages may merit re-assessment and we provide suggestions on how to approach future dating efforts.